气相二氧化硅的异氰酸酯改性及其对浇注型聚氨酯弹性体力学性能的影响

周鑫; 易玉华

doi:10.13801/j.cnki.fhclxb.20220303.002

气相二氧化硅的异氰酸酯改性及其对浇注型聚氨酯弹性体力学性能的影响

doi: 10.13801/j.cnki.fhclxb.20220303.002

周鑫,
易玉华^,

华南理工大学　机械与汽车工程学院，广州 510640

基金项目: 广州市科技计划项目(202102080477)Guangzhou Science and Technology Plan Project (202102080477)

详细信息

通讯作者:
易玉华，硕士，高级工程师，硕士生导师，研究方向为橡塑改性及其复合材料　E-mail: mmyhyi@scut.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-01-11
- 修回日期: 2022-02-17
- 录用日期: 2022-02-26
- 网络出版日期: 2022-03-06
- 刊出日期: 2023-02-15

Isocyanate modified fumed silica and its effects on the mechanical properties of casting polyurethane elastomer

ZHOU Xin,
YI Yuhua^,

School of Mechanical & Automotive Engineering, South China University of Technology, Guangzhou 510640, China

摘要

摘要: 为了改善气相二氧化硅(FS)/浇注型聚氨酯(PU)体系成型流动性，在制备预聚体的过程中，采用2, 4-甲苯二异氰酸酯(TDI)进行改性获得异氰酸酯改性的二氧化硅(NCO@FS)，通过原位聚合法制备了NCO@FS/PU弹性体复合材料。采用FTIR、XPS及动态接触角对NCO@FS及FS进行了表征。结果表明：FS的表面羟基与TDI的—NCO基团发生反应生成了氨酯基(—NHCOO)，改善了FS与PU间的界面相容性及界面结合。复合材料中NCO@FS质量分数为1.5wt%时，NCO@FS/PU复合材料的拉伸和撕裂强度分别为57 MPa和110.5 kN/m，比纯浇注型PU分别提高了31.6%和23.6%；玻璃化转变温度由3.4℃下降到−11.2℃，损耗因子tanδ由0.59下降到0.46。异氰酸酯改性FS适合制备FS增强浇注型聚氨酯复合材料。
- 异氰酸酯改性 /
- 气相二氧化硅 /
- 聚氨酯 /
- 复合材料 /
- 力学性能
Abstract: In order to improve the molding fluidity of fumed silica (FS)/cast polyurethane (PU) system, in the process of preparing prepolymer, the fumed silica (FS) was modified by 2, 4-toluene diisocyanate (TDI) to obtain TDI modified silica (NCO@FS), and TDI modified silica/reinforced pouring polyurethane (NCO@FS/PU) elastomer composite material was prepared by in-situ polymerization. NCO@FS and FS were characterized by fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and contact angle testing. The results show that the active hydroxyl groups on the surface of FS react with the —NCO groups of TDI to form urethane groups aminoester group (—NHCOO), which improves the interfacial compatibility and interfacial bonding between silica and casting polyurethane. When the mass fraction of NCO@FS in the composite material is 1.5wt%, the tensile and tearing strengths of the NCO@FS/PU composite material are 57 MPa and 110.5 kN/m, respectively, which are 31.6% and 23.6% higher than that of pure casting PU. The glass transition temperature dropped from 3.4°C to –11.2°C, and the loss factor tanδ dropped from 0.59 to 0.46. TDI modified fumed silica is suitable for preparing silica-reinforced cast polyurethane composites.
- isocyanate modification /
- fumed silica /
- polyurethane /
- composites /
- mechanical properties

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图 1 主要原材料结构式

Figure 1. Structural formula of main raw materials

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图 2 FS、2, 4-甲苯二异氰酸酯(TDI)和TDI改性的二氧化硅(NCO@FS)的FTIR图谱

Figure 2. FTIR spectra of FS, 2, 4-toluene diisocyanate (TDI) and TDI modified silica (NCO@FS)

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图 3 FS的原位异氰酸酯改性及增强PU机制

Figure 3. In situ isocyanate modification of FS and its mechanism schematic of reinforcing PU

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图 4 FS和NCO@FS的XPS图谱

Figure 4. XPS spectra of FS and NCO@FS

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图 5 FS和NCO@FS的Si2p高分辨XPS图谱

Figure 5. High-resolution XPS spectra of Si2p for FS and NCO@FS

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图 6 FS和NCO@FS的水 (a) 和PU预聚体 (b) 接触角

Figure 6. Contact angle of FS and NCO@FS with water (a) and PU prepolymer (b)

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图 7 不同FS含量的NCO@FS/PU复合材料的动态热机械分析(DMA)曲线：(a) 储能模量与温度曲线；(b) 损耗因子与温度曲线

Figure 7. Dynamic mechanical analysis (DMA) curves of NCO@FS/PU composites with different FS loading: (a) Storage modulus versus temperature; (b) Loss factor versus temperature

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图 8 FS/PU和NCO@FS/PU复合材料界面形貌

Figure 8. Interface morphologies of the FS/PU and NCO@FS/PU composites

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图 9 不同PU体系黏度对比

Figure 9. Comparison of viscosity for different PU systems

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表 1 不同2, 4-甲苯二异氰酸酯改性的二氧化硅(NCO@FS)和气相二氧化硅(FS)含量的聚氨酯 (PU)试样

Table 1. Polyurethane (PU) samples with different content of 2, 4-toluene diisocyanate modified silica (NCO@FS) and fumed silica (FS)

Sample	NCO@FS/wt%	FS/wt%
NCO@FS/PU-0.5	0.5	–
NCO@FS/PU-1.0	1.0	–
NCO@FS/PU-1.5	1.5	–
NCO@FS/PU-3.0	3.0	–
FS/PU-1.0	–	1.0
FS/PU-1.5	–	1.5
FS/PU-3.0	–	3.0

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表 2 FS和NCO@FS的XPS图谱中元素含量比较

Table 2. XPS atomic content for elements in FS and NCO@FS

System	C/at%	O/at%	Si/at%	N/at%	C/Si	O/Si
FS	45.74	38.03	16.23	0.00	2.82	2.34
NCO@FS	71.96	14.06	4.89	9.09	14.72	2.88

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表 3 FS/PU和NCO@FS/PU复合材料力学性能随FS质量分数的变化

Table 3. Variations in mechanical properties of FS/PU and NCO@FS/PU with the mass fraction of FS

Sample	Tensile strength /MPa	Tear strength /(kN·m⁻¹)	Elongation at break/%	Hardness (Shore D)
PU	43.3(0.9)	89.4(1.6)	447(10)	40(1)
NCO@FS/PU-0.5	45.4(1.3)	88.7(1.9)	424(18)	41(1)
NCO@FS/PU-1	51.6(1.0)	95.1(2.3)	576(14)	43(1)
NCO@FS/PU-1.5	57.0(0.8)	110.5(1.3)	516(10)	43(1)
NCO@FS/PU-3	17.7(1.5)	87.2(2.9)	303(23)	43(1)
FS/PU-1	47.7(0.8)	82.8(2.0)	459(15)	40(1)
FS/PU-1.5	28.0(0.6)	51.9(1.3)	478(20)	41(1)
FS/PU-3	7.9(1.2)	36.3(2.6)	243(21)	42(2)

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